114
J.D. Rose et al. / Carbohydrate Research 337 (2002) 105–120
ꢀ45 °C. MS (with LiCl): m/z 1547 [M+Li]+. UV
(EtOH, turbid at pH 1 and 7): 0.1 N HCl 246, 277 (sh),
285 (sh); pH 7 buffer 244, 277 (sh), 285 (sh); 0.1 N
NaOH 232 (69.2), 275 (8.15), 284 (sh). 1H NMR
(CDCl3): l 0. 88 (t, 6 H, CH3), 1.24, 1.42, 1.78, 2.96
(4m, 48 H, 4 H, 4 H, 4 H, aliphatic CH2), 2.60, 2.88
(2m, 4 H, J5,6 3.5, J6,6% 14.4, J6,NH 6.5, J5,6% 2.5, J6%,NH 6.5
Hz, 6-CH2), 3.93 (2m, 2 H, J4,5 10.0 Hz, H-5), 4.69
(app. t, 2 H, SO2NH), 5.32, 5.35 (2d, 2 H, J1,2 3.8, J2,3
10.2 Hz, H-2), 5.40 (app. t, 2 H, H-4, J3,4 9.8, J4,5 10.0
Hz, H-4), 5.71 (d, 2 H, H-1), 6.25 (app. t, 2 H, H-3),
7.32, 7.43, 7.59, 7.84, 7.92, 8.08 (complex m, 30 H, Bz).
Anal. Calcd for C86H112N2O19S2: C, 66.99; H, 7.32; N,
1.82; S, 4.16. Found: C, 67.23; H, 7.40; N, 1.75; S, 4.02.
2,3,4,2%,3%,4%-Hexa-O-benzoyl-6,6%-dideoxy-6,6%-
2-OH), 4.88 (d, 2 H, J 4.8 Hz, 3-OH), 4.93 (app. d, 4 H,
H-1 and 4-OH), 6.80 (app. t, 2 H, SO2NH). Anal.
Calcd for C20H40N2O13S2: C, 41.37; H, 6.94; N, 4.82.
Found: C, 41.16; H, 7.19; N, 4.62.
6,6% - Dideoxy - 6,6% - bis - [(1 - octylsulfonyl)amino] - h,h-
trehalose (11b).—Compound 10b (469 mg, 0.36 mmol)
was debenzoylated by the procedure given in detail for
11a The product was recrystallized from 2:1 water–
EtOH (30 mL), collected, washed on the funnel with
water and Et2O, and dried at 82 °C for 20 h; yield 204
mg (82%), mp 187–188 °C with prior sintering. MS
1
(with LiCl): m/z 699 [M+Li]+. H NMR (Me2SO-d6):
l 0.86 (t, 6 H, CH3), 1.26, 1.34, 1.64 (3m, 24 H,
aliphatic CH2), 2.99 (complex m, 8 H, CH2SO2NH+
H-4+6-CH), 3.26, 3.32 (m, 4 H, J1,2 3.6, J2,2-OH 5.8,
J2,3 9.6 Hz, 6-CH%+H-2), 3.55 (m, 2 H, J3,3-OH 4.8 Hz,
H-3), 3.74 (m, 2 H, J4,5 9.8, J5,6 1.8, J5,6% 6.7 Hz, H-5),
4.70 (d, 2 H, J2,2-OH 5.8 Hz, 2-OH), 4.86 (d, 2 H,
3-OH), 4.92 (m, 4 H, J4,4-OH 5.2 Hz, H-1+4-OH), 6.77
bis[(phenylsulfonyl)amino]-h,h-trehalose (10d).—Com-
pound 8 (1.00 g, 1.05 mmol) was reacted with
benzenesulfonyl chloride (389 mg, 1.05 mmol) by the
procedure given for 10a. Column chromatography on
silica gel with CHCl3 as eluant followed by drying for
20 h gave 10d as a brittle white foam; yield 1.10 g (84%)
mp softens gradually above ꢀ110 °C. MS: m/z 1245
[M+H]+, with LiCl 1251 [M+Li]+. UV (EtOH, tur-
bid at pH 1and 7): 0.1 N HCl 234, 273 (sh), 284 (sh);
pH 7 buffer 234, 273 (sh), 284 (sh); 0.1 N NaOH 231
(app. t,
2
H, SO2NH). Anal. Calcd for
C28H56N2O13S2·0.5 H2O: C, 47.91; H, 8.18; N, 3.99.
Found: C, 48.04; H, 8.28; N, 3.97.
6,6% - Dideoxy - 6,6% - bis[(1 - hexadecylsulfonyl)amino] -
h,h-trehalose (11c).—Compound 10c (774 mg, 0.50
mmol) was debenzoylated by the method of 11a, above,
except that a white solid deposited after ꢀ15 min in
the alkaline MeOH solution. The collected solid was
washed with Et2O (20 mL), suspended in 1:1 MeOH–
water (20 mL), and adjusted to pH 6.5 with HCl. The
solid was collected (350 mg, 76%) and recrystallized
from 9:1 MeOH–water (20 mL) to give a homogeneous
(TLC) first crop (172 mg, 37%, mp 185–186 °C) and a
lower-melting second crop (101 mg, 22%). After drying
at 82 °C for 20 h, the first crop was used as the
analytical sample. MS (with LiCl): m/z 923 [M+Li]+.
1H NMR (Me2SO-d6): l 0.86 (t, 6 H, CH3), 1.24, 1.34,
1.63 (4m, 24 H, 4 H, 4 H, aliphatic CH2), 2.99 (complex
m, 8 H, CH2SO2+H-4+6-CH), 3.26, 3.32 (complex
m, 4 H, J1,2 3.6, J2,3 9.8, J2,2-OH 4.8 Hz, H-2 overlapped
by 6-CH%), 3.55 (m, 2 H, J3,3-OH 4.8, J3,4 8.5 Hz, H-3),
3.73 (m, 2 H, H-5), 4.71(d, 2 H, J 5.8 Hz, OH-2), 4.86
(d, 2 H, 3-OH), 4.92 (app. d, 4 H, J1,2 3.6, J4,4-OH 4.9
Hz, H-1+4-OH), 6.78 (app. t, 2 H, SO2NHCH2).
Anal. Calcd for C44H88N2O13S2·0.2 H2O: C, 57.39; H,
9.68; N, 3.04. Found: C, 57.35; H, 10.02; N, 3.01.
6,6% - Dideoxy - 6,6% - bis[(phenylsulfonyl)amino] - h,h-
trehalose (11d).—Compound 10d (1.02 g, 0.82 mmol)
was debenzoylated by the procedure for 11a. The crude
product (500 mg, 98%) was recrystallized from a mix-
ture of boiling EtOH (25 mL) and water (3 mL). The
solid was collected, washed with EtOH, and dried at
82 °C for 20 h; yield 444 mg (86%); mp 217–218 °C.
MS (with LiCl): m/z 627 [M+Li]+. UV (EtOH): 0.1 N
HCl 220 (19.0), 264 (1.77), 271 (1.46); pH 7 buffer 220
1
(69.7) 273 (8.46), 284 (sh). H NMR (CDCl3): l 2.48,
2.75 (2m, 4 H, J5,6 4.5, J6,6% 14.4, J6,NH 6.1, J5,6% 2.5,
J6%,NH 7.3 Hz, 6-CH2), 3.83 (2m, 2 H, H-5), 4.97 (app. t,
2 H, SO2NH), 5.07 (dd, 2 H, J1,2 3.7, J2,3 10.3 Hz,
H-2,), 5.26 (dd, 2 H, J3,4 9.5, J4,5 10.2 Hz, H-4), 5.31 (d,
2 H, H-1), 6.11 (app. t, 2 H, H-3), 7.4, 7.77, 7.88, 8.03
(complex m, 35 H, Bz and Ph). Anal. Calcd for
C66H56N2O19S2: C, 63.66; H, 4.53; N, 2.25. Found: C,
63.54; H, 4.50; N, 1.99.
6,6% - Bis[(1 - butylsulfonyl)amino] - 6,6% - dideoxy - h,h-
trehalose (11a).—A solution of NaOMe in MeOH (0.21
mL of 1.74 N, 0.36 mmol) was added to a solution of
10a (430 mg, 0.36 mmol) in dry MeOH (10 mL), and
the solution was allowed to stand under N2 for 1 h. The
solution was diluted with an equal volume of water and
adjusted to pH 5 by portionwise addition of Dowex
50W-X8 (H+) cation exchange resin. The mixture was
filtered, and the filtrate was evaporated to dryness. The
residue was washed by trituration and filtration with
Et2O to extract methyl benzoate. The solid filter cake
(198 mg) was recrystallized from isopropyl alcohol (20
mL); the white solid was collected by filtration, washed
with 2-PrOH, and dried at 65 °C for 20 h; yield 163 mg
(79%); mp 169–170 °C. MS: m/z 581 [M+H]+, 563
[M–OH]+, 282 (1/2[M−16]+), 1161 [2M+H]+. 1H
NMR (Me2SO-d6): l 0.89 (t, 6 H, CH3), 1.38, 1.64 (2m,
4 each, aliphatic CH2), 3.03 (m, 8 H, CH2SO2NH
overlapped by 6-CH2), 3.28 (m, 2 H, J1,2 3.6, J2,3 9.8,
J2,2-OH 5.7 Hz, H-2), 3.31 (m, 2 H, H-4 overlapped by
water), 3.55 (m, 2 H, J3,4 10.0) Hz, H-3, 3.75 (m, 2 H,
J5,6 2.2, J5,6% 6.5 Hz, H-5), 4.73 (d, 2 H, J 5.7 Hz,
1
(18.5), 264 (1.56), 272 (1.28); 0.1 N NaOH 236 (sh). H
NMR (Me2SO-d6): l 2.77 (m, 2 H, J5,6 7.3, J6,6% 12.8,